Semiconductor device including storage node electrode including step and method of manufacturing the semiconductor device

ABSTRACT

A semiconductor device may include a bottom sub-electrode on a substrate, a top sub-electrode on the bottom sub-electrode, a dielectric layer covering the bottom and top sub-electrodes, and a plate electrode on the dielectric layer. The top sub-electrode may include a step extending from a side surface thereof, which is adjacent to the bottom sub-electrode, to an inner portion of the top sub-electrode. The top sub-electrode may include a lower portion at a level that is lower than the step and an upper portion at a level which is higher than the step. A maximum width of the lower portion may be narrower than a minimum width of the upper portion. The maximum width of the lower portion may be narrower than a width of a top end of the bottom sub-electrode. The bottom sub-electrode may include a recess in a region adjacent to the top sub-electrode.

CROSS-REFERENCE TO THE RELATED APPLICATION

This application is a divisional of U.S. application Ser. No.16/943,019, filed Jul. 30, 2020, which claims priority from KoreanPatent Application No. 10-2019-0179040, filed Dec. 31, 2019, in theKorean Intellectual Property Office, the disclosure of each of which isincorporated herein by reference in its entirety.

BACKGROUND 1. Field

Apparatuses and methods consistent with example embodiments relate to asemiconductor device including a storage node electrode including a stepand/or a method of manufacturing the semiconductor device.

2. Description of Related Art

As semiconductor devices are increasing in degree of integration and arebeing miniaturized, capacitors of dynamic random access memory (DRAM)devices are increasing in aspect ratio so as to provide a highcapacitance in a limited area. Therefore, double storage node electrodetechnology for vertically stacking storage node electrodes to increase acapacitance is being developed.

Semiconductor devices include a supporter pattern, and thus, support astorage node electrode having a high aspect ratio so as not to fall.However, in a double storage node electrode, when a top storage nodeelectrode disposed at an upper portion is misaligned with respect to abottom storage node electrode disposed at a lower portion, the topstorage node electrode extends to an open region of the supporterpattern, an may cause a reliability error in capacitors. Also, adefective connection where the top storage node electrode contacts aplurality of bottom storage node electrodes may occur.

SUMMARY

Some example embodiments of inventive concepts are directed to asemiconductor device including a double storage node electrode withenhanced reliability.

In addition, some example embodiments of inventive concepts are directedto a method of manufacturing a semiconductor device including a doublestorage node electrode with enhanced reliability.

A semiconductor device according to an embodiment of inventive conceptsmay include a substrate, a bottom sub-electrode on the substrate, a topsub-electrode on the bottom sub-electrode, a dielectric layer coveringthe bottom sub-electrode and the top sub-electrode, and a plateelectrode on the dielectric layer. A region of the bottom sub-electrodemay include a recess. The top sub-electrode may include a step extendingfrom a side surface thereof. The step of the top sub-electrode may beadjacent to the bottom sub-electrode and an inner portion of the topsub-electrode. The top sub-electrode may include a lower portion at alevel lower than the step of the top sub-electrode and an upper portionat a level higher than the step of the top sub-electrode. A maximumwidth of the lower portion of the top sub-electrode may be narrower thana minimum width of the upper portion of the top sub-electrode. Themaximum width of the lower portion of the top sub-electrode may benarrower than a width of a top end of the bottom sub-electrode. The topsub-electrode may be adjacent to the region of the bottom sub-electrodeincluding the recess.

A semiconductor device according to an embodiment of inventive conceptsmay include a substrate, a storage node electrode on the substrate, adielectric layer covering a surface of the storage node electrode, aplate electrode on the dielectric layer, and a supporter patterncovering a portion of a side surface of the storage node electrode. Thestorage node electrode may include a bottom sub-electrode and a topsub-electrode on the bottom sub-electrode. The top sub-electrode mayinclude a step in a side surface thereof adjacent to the bottomsub-electrode. The bottom sub-electrode may include a recess in a sidesurface thereof adjacent to the top sub-electrode. The supporter patternmay include a lower supporter pattern contacting the recess of thebottom sub-electrode.

A method of manufacturing a semiconductor device may include forming abottom sub-electrode on a substrate; forming a lower supporter patterncovering a portion of a side surface of the bottom sub-electrode;forming an etch stop layer covering a top surface of the lower supporterpattern and a top surface of the bottom sub-electrode, the etch stoplayer including a filler part extending up to a level that is lower thana bottom end of the lower supporter pattern; forming a mold layer on theetch stop layer; planarizing the etch stop layer and the mold layer;forming a top mold structure on the etch stop layer; forming a topstorage node electrode hole passing through the etch stop layer and thetop mold structure, the top storage node electrode hole exposing the topsurface of the bottom sub-electrode; forming a top sub-electrode fillingthe top storage node electrode hole, the top sub-electrode including astep extending in a direction toward an inner portion thereof; andremoving the etch stop layer.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a plan view illustrating an upper supporter pattern 70 andstorage node electrodes 40 and 80 of a semiconductor device according toan embodiment.

FIG. 2 is a vertical cross-sectional view taken along line I-I of FIG. 1for schematically illustrating the semiconductor device according to anembodiment.

FIGS. 3A and 3B are enlarged cross-sectional views of a region P1 ofFIG. 2 according to an embodiment.

FIG. 3C is an enlarged cross-sectional view of a region P2 of FIG. 2according to an embodiment.

FIG. 4 is a vertical cross-sectional view taken along line I-I of FIG. 1for schematically illustrating a semiconductor device according to anembodiment.

FIGS. 5 and 6 are vertical cross-sectional views taken along line I-I ofFIG. 1 for schematically illustrating a semiconductor device accordingto an embodiment.

FIG. 7 is a vertical cross-sectional view taken along line I-I of FIG. 1for schematically illustrating a semiconductor device according to anembodiment.

FIG. 8 is a vertical cross-sectional view taken along line I-I of FIG. 1for schematically illustrating a semiconductor device according to anembodiment.

FIGS. 9 to 25 are vertical cross-sectional surfaces for describing amethod of manufacturing a semiconductor device, according to anembodiment.

DETAILED DESCRIPTION

FIG. 1 is a plan view illustrating an upper supporter pattern 70 andstorage node electrodes 40 and 80 of a semiconductor device according toan embodiment. FIG. 2 is a vertical cross-sectional view taken alongline I-I of FIG. 1 for schematically illustrating the semiconductordevice according to an embodiment. FIGS. 3A and 3B are enlargedcross-sectional views of a region P1 of FIG. 2 according to anembodiment. FIG. 3C is an enlarged cross-sectional view of a region P2of FIG. 2 according to an embodiment.

Referring to FIGS. 1 and 2 , the semiconductor device may include asubstrate 10, a lower etch stop layer ESL, a lower supporter pattern 30,a plurality of storage node electrodes 40 and 80, an upper supporterpattern 70, a dielectric layer 90, and a plate electrode 100.

The substrate 10 may include a semiconductor substrate such as a siliconwafer. The substrate 10 may include a cell region where a plurality ofmemory cells are provided and a core/peri region which controls thememory cells. A plurality of semiconductor devices provided in the cellregion of the substrate 10 may each include a lower structure 11 and aconnection structure 12. For example, the lower structure 11 may includea source/drain region, and the connection structure 12 may include astorage node contact and/or a landing pad. The connection structure 12may be electrically divided by an interlayer insulation layer on thesubstrate 10.

The lower etch stop layer ESL may be disposed on the substrate 10. Thelower etch stop layer ESL may be disposed on the interlayer insulationlayer 13 and may expose a top surface of the connection structure 12.For example, the lower etch stop layer ESL may include, like siliconoxide (SiN) or silicon oxynitride (SiON), a material having etchselectivity with respect to silicon oxide (SiO₂).

The storage node electrodes 40 and 80 may be disposed on the substrate10. The storage node electrodes 40 and 80, as illustrated in FIG. 1 ,may be repeatedly arranged in a first direction D1 and a seconddirection D2. The storage node electrodes 40 and 80 may be formed in ahoneycomb structure where the storage node electrodes 40 and 80 arearranged to be staggered with respect to storage node electrodes 40 and80 of adjacent rows or columns. When the storage node electrodes 40 and80 are arranged to be staggered in zigzag, a distance between adjacentstorage node electrodes 40 and 80 may be constant. In an embodiment, thestorage node electrodes 40 and 80 may be arranged in a lattice patternalong a column direction and a row direction.

The storage node electrodes 40 and 80 may be electrically connected tothe connection structure 12. The storage node electrodes 40 and 80 maydirectly contact a top surface of the connection structure 12 (forexample, a landing pad of DRAM). The storage node electrodes 40 and 80may have a pillar shape and/or a cylindrical shape. The storage nodeelectrodes 40 and 80 may include metal or a metal compound. For example,the storage node electrodes 40 and 80 may include at least one of metalnitrides such as titanium nitride (TiN), titanium silicon nitride(TiSiN), titanium aluminium nitride (TiAlN), tantalum aluminium nitride(TaAlN), and tungsten nitride (WN).

The storage node electrodes 40 and 80 may each have a multi-layerstructure. The storage node electrodes 40 and 80 may include a bottomsub-electrode 40 and a top sub-electrode 80, which are verticallystacked on the substrate 10. The bottom sub-electrode 40 may be disposedon the connection structure 12, and the top sub-electrode 80 may bedisposed on the bottom sub-electrode 40. The top sub-electrode 80 maycontact the bottom sub-electrode 40 and may be electrically connectedthereto.

The supporter patterns 30 and 70 may be disposed in contact with sidesurfaces of the storage node electrodes 40 and 80, respectively, and maysupport the storage node electrodes 40 and 80 so as not to fall. Thesupporter patterns 30 and 70 may include the lower supporter pattern 30contacting a portion of a side surface of the bottom sub-electrode 40and the upper supporter pattern 70 contacting a portion of a sidesurface of the top sub-electrode 80.

The lower supporter pattern 30 may include a first lower supporterpattern 31 and a second lower supporter pattern 39. The first lowersupporter pattern 31 may cover a portion of the side surface of thebottom sub-electrode 40. The second lower supporter pattern 39 may bedisposed at a level which is higher than the first lower supporterpattern 31. The second lower supporter pattern 39 may contact an upperside surface of the bottom sub-electrode 40.

The upper supporter pattern 70 may include a first upper supporterpattern 71 and a second upper supporter pattern 73. The first uppersupporter pattern 71 may cover a portion of the side surface of the topsub-electrode 80. The second upper supporter pattern 73 may contact anupper side surface of the top sub-electrode 80.

The dielectric layer 90 may be disposed on the storage node electrodes40 and 80. The dielectric layer 90 may conformally cover a surface ofthe bottom sub-electrode 40, a surface of the lower supporter pattern30, a surface of the top sub-electrode 80, a surface of the uppersupporter pattern 70, and a surface of the lower etch stop layer ESL.

The dielectric layer 90 may include at least one of metal oxides such ashafnium oxide (Hf_(x)O_(y)), aluminium oxide (Al_(x)O_(y)), titaniumoxide (Ti_(x)O_(y)), tantalum oxide (Ta_(x)O_(y)), ruthenium oxide(Ru_(x)O_(y)), lanthanum oxide (La_(x)O_(y)), or zirconium oxide (ZrO₂),a dielectric material having a perovskite structure such as SrTiO₃(STO),(Ba, Sr)TiO₃(BST), BaTiO₃, lead zirconate titanate (PZT), lead lanthanumzirconium titanate (PLZT), silicon oxide, and silicon nitride.

The plate electrode 100 may be disposed on the dielectric layer 90. Theplate electrode 100 may include a top plate electrode 103 and a bottomplate electrode 101. The bottom plate electrode 101 may be formed toconformally cover the dielectric layer 90. The top plate electrode 103may be disposed on the bottom plate electrode 101. The top plateelectrode 103 may fill a spare space between the bottom plate electrode101, remaining after the bottom plate electrode 101 is formed,

For example, the bottom plate electrode 101 may include at least one ofmetal nitrides such as TiN, TiSiN, TiAlN, TaAlN, and WN. In anembodiment, the bottom plate electrode 101 may include the same materialas that of each of the storage node electrodes 40 and 80. The top plateelectrode 103 may include silicon germanium (SiGe).

Referring to FIGS. 2 and 3A, in an embodiment, the bottom sub-electrode40 may include an external bottom sub-electrode 41 a, and the topsub-electrode 80 may include an external top sub-electrode 81 a. Theexternal bottom sub-electrode 41 a and the external top sub-electrode 81a may each have a vertical cross-sectional surface having a symmetricalstructure. The external top sub-electrode 81 a may be stacked on theexternal bottom sub-electrode 41 a.

An upper side surface of the external bottom sub-electrode 41 a adjacentto the external top sub-electrode 81 a may include a recess RC. Therecess RC may have a concave shape where a side surface of the externalbottom sub-electrode 41 a is inward recessed. The external bottomsub-electrode 41 a may include an upper portion 41 a-u including therecess RC and a lower portion 41 a-d disposed at a level which is lowerthan the recess RC. A minimum width wu of the upper portion 41 a-uincluding the recess RC may be narrower than a maximum width wd of a topend of the lower portion 41 a-d.

The external top sub-electrode 81 a may include a step ST which extendsfrom a side surface thereof, which is adjacent to the external bottomsub-electrode 41 a, to an inner portion of the external topsub-electrode 81 a. The step ST may have a stepped structure and mayhave a side profile where a width of the external bottom sub-electrode41 a is narrowed. The external top sub-electrode 81 a may include alower portion 81 a-d, disposed at a level which is lower than the stepST, and an upper portion 81 a-u disposed at a level which is higher thanthe step ST. A maximum width wb of the lower portion 81 a-d may benarrower than a minimum width wa of the upper portion 81 a-u. Themaximum width wb of the lower portion 81 a-d may be less than a width ofa top end of the external bottom sub-electrode 41 a.

The external top sub-electrode 81 a may be vertically aligned with theexternal bottom sub-electrode 41 a, and thus, a bottom surface of theexternal top sub-electrode 81 a may contact a top surface of theexternal bottom sub-electrode 41 a and a portion of the top surface ofthe external bottom sub-electrode 41 a may be exposed. The external topsub-electrode 81 a may be apart from the second lower supporter pattern39 without contact therebetween.

The second lower supporter pattern 39 may include an overhang OHvertically overlapping the bottom sub-electrode 40. The overhang OH ofthe second lower supporter pattern 39 may contact the recess RC of thesecond lower supporter pattern 39. The second lower supporter pattern 39may include a flat top surface. A level of the top surface of the secondlower supporter pattern 39 may be the same as that of a top end of thebottom sub-electrode 40.

The second lower supporter pattern 39 may include a round side surface.That is, an outer surface of the overhang OH may include a round sidesurface. Therefore, the second lower supporter pattern 39 may have around shape which is rounded to be convex toward the upper portion 81a-u of the bottom sub-electrode 40. The round side surface of the secondlower supporter pattern 39 may contact the recess RC of the bottomsub-electrode 40.

The bottom plate electrode 101 may include a side protrusion portionPU_S at a side surface thereof adjacent to the step ST of the topsub-electrode 80. The side protrusion portion PU_S may extend outwardtoward the lower portion 81 a-d of the top sub-electrode 80, and thebottom plate electrode 101 may have a side profile where a widthincreases in a lower portion thereof. The side protrusion portion PU_Smay be disposed between the step ST of the top sub-electrode 80 and thetop surface of the bottom sub-electrode 40 exposed by the lower portion81 a-d of the top sub-electrode 80. In a top view, the side protrusionportion PU_S may have a ring shape.

Referring to FIGS. 2 and 3B, in an embodiment, the recess RS of theexternal bottom sub-electrode 41 a may be a positive (+) inclinedsurface which extends upward toward an inner portion thereof. The upperportion 40 a-u of the bottom sub-electrode 40 of a region adjacent tothe top sub-electrode 80 may have a trapezoidal shape where a width of avertical cross-sectional surface thereof is progressively narrowed in anupward direction. The second lower supporter pattern 39 may have aninverted trapezoidal shape where a width thereof is progressivelywidened in an upward direction. A vertical cross-sectional surface ofthe overhang OH of the second lower supporter pattern 39 may have aninverted triangular shape.

Referring to FIGS. 2 and 3C, the top sub-electrode 80 may include aninternal bottom sub-electrode 41 b and an internal top sub-electrode 81b. The internal bottom sub-electrode 41 b and the internal topsub-electrode 81 b may each have a vertical cross-sectional surfacehaving an asymmetrical structure. The internal top sub-electrode 81 bmay be stacked on the internal bottom sub-electrode 41 b.

The internal bottom sub-electrode 41 b may include an inclined surfaceSS at a level which is higher than the first lower supporter pattern 31and may include a recess RC in a region adjacent to the internal topsub-electrode 41 a. The recess RC may be formed at a level which ishigher than a bottom end of the second lower supporter pattern 39. Therecess RC may contact the second lower supporter pattern 39, and theinclined surface SS may be covered by the internal top sub-electrode 81b and the dielectric layer 90.

The internal top sub-electrode 81 b may include a step ST having astepped structure at a lower side surface adjacent to the internalbottom sub-electrode 41 b. The internal top sub-electrode 81 b mayinclude a downward protrusion portion PU_D which extends in a downwarddirection from a portion of a bottom surface thereof. The downwardprotrusion portion PU_D may extend up to a level which is lower than atop end of the internal bottom sub-electrode 41 b. The downwardprotrusion portion PU_D may cover a portion of inclined surface SS ofthe internal bottom sub-electrode 41 b. The downward protrusion portionPU_D may be disposed between the inclined surface SS of the internalbottom sub-electrode 41 b and the dielectric layer 90.

FIG. 4 is a vertical cross-sectional view taken along line I-I of FIG. 1for schematically illustrating a semiconductor device according to anembodiment.

Referring to FIG. 4 , in an embodiment, an external bottom sub-electrode41 a may have a wholly flat side profile. The second lower supporterpattern 39 may also have a flat side profile and may not include anoverhang OH.

An internal bottom sub-electrode 41 b may include an inclined surface SSwith respect to an upper side surface thereof adjacent to a topsub-electrode 80. The inclined surface SS may have an inclined profilewith respect to a top surface of a substrate 10. A downward protrusionportion PU_D of an internal top sub-electrode 81 b may cover a portionof the inclined surface SS of the internal bottom sub-electrode 41 b.The downward protrusion portion PU_D may extend in a downward directionalong the inclined surface SS of the internal bottom sub-electrode 41 band may have an inverted triangular shape where a width thereof isprogressively narrowed toward a downward direction.

FIGS. 5 and 6 are vertical cross-sectional views taken along line I-I ofFIG. 1 for schematically illustrating a semiconductor device accordingto an embodiment.

Referring to FIGS. 5 and 6 , a top sub-electrode 80 may be misalignedwith respect to a bottom sub-electrode 40. An external top sub-electrode81 a may be disposed on an internal bottom sub-electrode 41 b as well asan external bottom sub-electrode 41 a.

A bottom surface of the external top sub-electrode 81 a disposed on theexternal bottom sub-electrode 41 a may contact a top surface of each ofthe bottom sub-electrode 40 and a second lower supporter pattern 39. Abottom surface of the external top sub-electrode 81 a disposed on theinternal bottom sub-electrode 41 b may contact a top surface of theinternal bottom sub-electrode 41 b and the top surface of the secondlower supporter pattern 39.

A downward protrusion portion PU_D of an internal top sub-electrode 81 bmay contact an inclined surface SS of the internal bottom sub-electrode41 b and may not contact the top surface of the internal bottomsub-electrode 41 b.

FIG. 7 is a vertical cross-sectional view taken along line I-I of FIG. 1for schematically illustrating a semiconductor device according to anembodiment. FIG. 8 is a vertical cross-sectional view taken along lineI-I of FIG. 1 for schematically illustrating a semiconductor deviceaccording to an embodiment.

Referring to FIGS. 7 and 8 , a top sub-electrode 80 may have a whollyflat side profile at a level which is higher than a top end of a secondlower supporter pattern 39. The top sub-electrode 80 may not include astep ST.

FIGS. 9 to 25 are vertical cross-sectional surfaces for describing amethod of manufacturing a semiconductor device, according to anembodiment.

Referring to FIG. 9 , the method may include a process of providing asubstrate 10, a process of forming a bottom mold structure on theprovided substrate 10, and a process of forming a mask pattern MP on thebottom mold structure.

The process of forming the bottom mold structure may include a processof sequentially forming a lower etch stop layer ESL, a first bottom moldlayer 21, a first lower supporter layer 31 a, a second bottom mold layer23, and a second lower supporter layer 33 a on the substrate 10.

The lower etch stop layer ESL may be formed to wholly cover a topsurface of the substrate 10. For example, the lower etch stop layer ESLmay include SiN or SiON.

The first bottom mold layer 21 and the second bottom mold layer 23 mayinclude a material having etch selectivity with respect to the loweretch stop layer ESL and the first lower supporter layer 31 a. Forexample, the first bottom mold layer 21 and the second bottom mold layer23 may include SiO₂. The first lower supporter layer 31 a may include atleast one of SiN, SiON, and silicon carbonitride (SiCN).

The second lower supporter layer 33 a may include a material having etchselectivity with respect to the second bottom mold layer 23. In anembodiment, the second lower supporter layer 33 a may include a materialwhere step coverage is bad. For example, the second lower supporterlayer 33 a may include at least one of SiCN and silicon boron nitride(SiBN).

The mask pattern MP may be formed on the second lower supporter layer 33a. A mask layer covering the second lower supporter layer 33 a may beformed, and the mask pattern MP may be formed by patterning the masklayer, whereby a top surface of the second lower supporter layer 33 amay be selectively exposed. The mask pattern MP may include a materialhaving etch selectivity with respect to the second lower supporter layer33 a. For example, the mask pattern MP may include at least one of apolysilicon layer, an amorphous silicon layer, a silicon oxide layer, asilicon oxynitride layer, a spin on hard (SOH) mask layer, and a polymerorganic material layer.

Referring to FIG. 10 , the method may include a process of forming abottom storage node electrode hole H1 passing through the bottom moldstructure. The bottom storage node electrode hole H1 may pass throughthe lower etch stop layer ESL, the first bottom mold layer 21, the firstlower supporter layer 31 a, the second bottom mold layer 23, and thesecond lower supporter layer 33 a of the bottom mold structure. Thebottom storage node electrode hole H1 may expose a connection structure12 of the substrate 10. The bottom storage node electrode hole H1 may beformed by an etch process using the mask pattern MP as an etch mask. Thebottom storage node electrode hole H1 may be formed by an anisotropicetch process. As the bottom storage node electrode hole H1 is formed, afirst preliminary lower supporter pattern 31P may be formed bypatterning the first lower supporter layer 31 a, and a secondpreliminary lower supporter pattern 33P may be formed by patterning thesecond lower supporter layer 33 a. The bottom storage node electrodehole H1 may be formed, and the mask pattern MP may be removed.

The bottom storage node electrode hole H1 may have a certain width. Inan embodiment, the bottom storage node electrode hole H1 may have atapered shape where a width thereof is narrowed toward the substrate 10.After the bottom storage node electrode hole H1 is formed, a cleaningprocess of removing impurities which occur in the process of forming thebottom storage node electrode hole H1 may be performed.

Referring to FIG. 11 , the method may include a process of forming abottom sub-electrode 40 and a second preliminary lower supporter pattern33 including an overhang OH. A lower capping layer 35 covering a surfaceof the second preliminary lower supporter pattern 33P may be formed, andthus, the second preliminary lower supporter pattern 33 including theoverhang OH may be formed. The lower capping layer 35 may be formed byusing a process such as a plasma enhanced chemical vapour deposition(PECVD) process, where step coverage is bad.

The lower capping layer 35 may not conformally be formed on the secondpreliminary lower supporter pattern 33P. For example, a thickness of thelower capping layer 35 formed on a top surface of the second preliminarylower supporter pattern 33P may be thicker than a thickness of the lowercapping layer 35 formed on a side surface of the second preliminarylower supporter pattern 33.

A thickness of the lower capping layer 35 on the side surface of thesecond preliminary lower supporter pattern 33P may not be uniform. Forexample, a thickness of the lower capping layer 35 covering the sidesurface of the second preliminary lower supporter pattern 33P may bethicker in an upper portion thereof than a lower portion thereof.Therefore, the surface of the second preliminary lower supporter pattern33P including the lower capping layer 35 may be formed convexly.

The lower capping layer 35 may include a material where step coverage isbad. In an embodiment, the lower capping layer 35 may include the samematerial as that of the second preliminary lower supporter pattern 33P.For example, the lower capping layer 35 may include at least one of SiCNand SiBN.

The bottom sub-electrode 40 may be formed to fill the bottom storagenode electrode hole H1. An electrode material layer filling the bottomstorage node electrode hole H1 and covering the second preliminary lowersupporter pattern 33P may be formed, and the bottom sub-electrode 40 maybe formed by removing a portion of the electrode material layer througha partial etch back process. A top end of the bottom sub-electrode 40may be disposed at a level which is equal to or lower than a top end ofthe second preliminary lower supporter pattern 33P.

The bottom sub-electrode 40 may include metal or metal nitride. Forexample, the bottom sub-electrode 40 may include TiN. The bottomsub-electrode 40 may be formed by a process such as a chemical vapordeposition (CVD) process, an atomic layer deposition (ALD) process, or aplasma enhanced atomic layer deposition (PEALD) process.

Referring to FIG. 12 , the method may include a process of planarizing atop surface of the second preliminary lower supporter pattern 33P and atop surface of the bottom sub-electrode 40. The top surface of thesecond preliminary lower supporter pattern 33P and a top surface of thebottom sub-electrode 40 may be coplanar, based on the planarizationprocess. Based on the planarization process, an upper portion of thelower capping layer 35 may be removed, and thus, the second lowersupporter layer 33 a may be exposed. For example, the planarizationprocess may be a chemical mechanical polishing (CMP) process.

Referring to FIG. 13 , the method may include a process of removing aportion of the second preliminary lower supporter pattern 33P to form asecond lower supporter pattern 39 and an opening portion OP.

A hard mask pattern HM exposing a portion of a top surface of the secondpreliminary lower supporter pattern 33P may be formed on the secondpreliminary lower supporter pattern 33P and the bottom sub-electrode 40.By performing an anisotropic etch process using the hard mask pattern HMas an etch mask, the exposed portion of the second preliminary lowersupporter pattern 33P may be removed, and the opening portion OP and thesecond lower supporter pattern 39 may be formed. In a process of formingthe opening portion OP, a portion of a side surface of the bottomsub-electrode 40 may be etched, and thus, the opening portion OP may beenlarged and an inclined surface SS may be formed at an upper portion ofthe side surface of the bottom sub-electrode 40.

The method may include a process of removing the second bottom moldlayer 23 to form a cavity CV and etching a portion of the firstpreliminary lower supporter pattern 31P to form a first lower supporterpattern 31. The second bottom mold layer 23 may be removed by performinga wet etch process. For example, a process of removing the second bottommold layer 23 may include a limulus amoebocyte lysate (LAL) process.

The opening portion OP may extend in a downward direction, and thecavity CV may be formed between the first preliminary lower supporterpattern 31P and the second lower supporter pattern 39. A portion of eachof a top surface of the first preliminary lower supporter pattern 31P, abottom surface of the second lower supporter pattern 39, and a sidesurface of the bottom sub-electrode 40 may be exposed through the cavityCV. By etching a portion of the first preliminary lower supporterpattern 31P exposed through the opening portion OP, the first lowersupporter pattern 31 may be formed, and a portion of the first bottommold layer 21 may be exposed. A portion of the first bottom mold layer21 may be etched in a process of forming the first lower supporterpattern 31. The first lower supporter pattern 31 may be formed, and thehard mask pattern HM may be removed.

Referring to FIG. 14 , the method may include a process of filling thecavity CV and the opening portion OP and forming a third bottom moldlayer 25 covering a top surface of the second lower supporter pattern 39and a top surface of the bottom sub-electrode 40. The third bottom moldlayer 25 may include the same material as that of the first bottom moldlayer 21. For example, the third bottom mold layer 25 may include SiO₂.The third bottom mold layer 25 may be formed by a process such as an ALDprocess, a CVD process, or a PEALD process.

Referring to FIG. 15 , the method may include a process of opening theopening portion OP again and forming an upper etch stop layer 50 fillingthe opening portion OP. By removing a portion of the third bottom moldlayer 25 through a partial etch back process, a top surface of each ofthe bottom sub-electrode 40 and the second lower supporter pattern 39may be exposed, and the opening portion OP may be opened again. Based onthe opening portion OP, the inclined surface SS of the bottomsub-electrode 40 may be exposed, and a portion of a top surface of thethird bottom mold layer 25 may be exposed. In a process of forming theopening portion OP, a portion of the inclined surface SS of the bottomsub-electrode 40 may be etched, and a size of the opening portion OP mayincrease.

The upper etch stop layer 50 may include a filler part 50 a which coversa top surface of each of the second lower supporter pattern 39 and thebottom sub-electrode 40 and partially fills the opening portion OP. Thefiller part 50 a may be formed to cover the inclined surface SS of thebottom sub-electrode 40 and the exposed portion of the third bottom moldlayer 25, in the opening portion OP. The filler part 50 a may extend upto a level which is lower than a bottom end of the second lowersupporter pattern 39. The filler part 50 a may have a U-shape or aV-shape, and even after the filler part 50 a is formed, a spare spacemay remain in the opening portion OP. In an LAL process, the upper etchstop layer 50 may include a material which has etch selectivity higherthan a lower supporter pattern 30 and an upper supporter pattern 70(which will be described below) and has etch selectivity equal to orlower than the third bottom mold layer 25. For example, the upper etchstop layer 50 may include bowing block SiN (B-SiN) or bowing block SiON(B-SiON). In an embodiment, the upper etch stop layer 50 may includepolysilicon (poly-Si).

Referring to FIG. 16 , the method may include a preliminary top moldlayer 27 covering a top surface of the upper etch stop layer 50. Thepreliminary top mold layer 27 may fill the spare space of the openingportion OP. For example, the preliminary top mold layer 27 may includeSiO₂. The preliminary top mold layer 27 may be formed by a process suchas a CVD process, an ALD process, or a PEALD process.

Referring to FIG. 17 , the method may include performing a planarizationprocess of exposing a top surface of the upper etch stop layer 50. Theplanarization process may planarize the top surface of the upper etchstop layer 50 and a top surface of the preliminary top mold layer 70.Based on the planarization process, the preliminary top mold layer 27may be removed, and thus, the preliminary top mold layer 27 may remainin only the opening portion OP. A thickness of the upper etch stop layer50 on the bottom sub-electrode 40 and the second lower supporter pattern39 may be thinned. For example, the planarization process may be a CMPprocess. In a process of manufacturing the semiconductor device, a hole(for example, a storage node electrode hole H1) or the opening portionOP may be formed to have a density which is higher in a cell region thana core/peri region. Therefore, a step height may occur between thepreliminary top mold layer 27 formed in the cell region and apreliminary top mold layer (not shown) formed in the core/peri region.The planarization process may remove a step height of the preliminarytop mold layer 27 formed in the cell region and the core/peri region,and at this time, the upper etch stop layer 50 may limit and/or preventthe height loss of the bottom sub-electrode 40.

Referring to FIG. 18 , the method may include a process of forming a topmold structure on the upper etch stop layer 50. The process of formingthe top mold structure may include a process of sequentially forming afirst top mold layer 61, a first upper supporter layer 71 a, a secondtop mold layer 63, and a second upper supporter layer 73 a on the upperetch stop layer 50. The process of forming the top mold structure may besimilar to the process of forming the bottom mold structure describedabove.

Referring to FIG. 19 , the method may include a process of forming a topstorage node electrode hole H2 passing through the top mold structure.The top storage node electrode hole H2 may pass through the first topmold layer 61, the first upper supporter layer 71 a, the second top moldlayer 63, the second upper supporter layer 73 a, and the upper etch stoplayer 50. The top storage node electrode hole H2 may expose the topsurface of the bottom sub-electrode 40. The top storage node electrodehole H2 may be formed by an etch process using the upper etch stop layer50 as an etch mask. As the top storage node electrode hole H2 is formed,a first preliminary upper supporter pattern 71P may be formed bypatterning the first upper supporter layer 71 a, and a secondpreliminary upper supporter pattern 73P may be formed by patterning thesecond upper supporter layer 73 a.

The top storage node electrode hole H2 may be formed to verticallyoverlap the bottom sub-electrode 40. A center of the top storage nodeelectrode hole H2 may be aligned with a center of the bottomsub-electrode 40. In an embodiment, the center of the top storage nodeelectrode hole H2 may be misaligned with the center of the bottomsub-electrode 40.

An anisotropic etch process of forming the top storage node electrodehole H2 may use the upper etch stop layer 50 for stopping etching. Aportion of the top surface of the upper etch stop layer 50 may berecessed by the anisotropic etch process.

Referring to FIG. 20 , the method may include a process of increasing awidth of the top storage node electrode hole H2 to form a steppedportion STP. A portion of the top mold structure may be etched in ahorizontal direction through a wet etch process using a diluted sulfuricacid peroxide (DSP) solution as an etchant, and thus, the width of thetop storage node electrode hole H2 may increase. Since the upper etchstop layer 50 is lower in etching rate than the top mold structure withrespect to the DSP solution, the upper etch stop layer 50 may be lowerin etching amount than the first bottom mold layer 21 of the top moldstructure. Therefore, the upper etch stop layer 50 may be formed in ashape which is offset with respect to an inner wall of the top storagenode electrode hole H2 limited by the first bottom mold layer 21.Accordingly, the stepped portion STP having a stepped structureincluding the top surface of the upper etch stop layer 50 may be formedunder the top storage node electrode hole H2.

In an embodiment, the top storage node electrode hole H2 may extend in adownward direction toward the filler part 50 a of the upper etch stoplayer 50 filling the opening portion OP. A portion of the filler part 50a adjacent to the inclined surface SS of the bottom sub-electrode 40 maybe etched by the anisotropic etch process of etching the upper etch stoplayer 50. Therefore, a portion of a bottom end of the top storage nodeelectrode hole H2 may extend, and thus, an extension region ER whichexposes the inclined surface SS of the bottom sub-electrode 40 and anouter surface of the filler part 50 a may be formed. The extensionregion ER may have a shape where a vertical length thereof is greaterthan a horizontal width thereof. In an embodiment, a level of a bottomend of the extension region ER may be disposed to be higher than a levelof a bottom surface of the second lower supporter pattern 39.

Referring to FIG. 21 , the method may further include a process offorming a second preliminary upper supporter pattern 73 including anoverhang. An upper capping layer 75 covering a surface of the secondpreliminary upper supporter pattern 73P may be formed, and thus, thesecond preliminary upper supporter pattern 73 including the overhang maybe formed. A process of forming the upper capping layer 75 may be thesame as or similar to the process of forming the lower capping layer 35.In an embodiment, the process of forming the upper capping layer 75 maybe omitted.

Referring to FIG. 22 , the method may include a process of forming a topsub-electrode 80 filling the top storage node electrodes 40 and 80. Theprocess of forming the top sub-electrode 80 may be the same as orsimilar to the process of forming the bottom sub-electrode 40 describedabove.

The top sub-electrode 80 may be formed along a profile of the steppedportion STP of the top storage node electrode hole H2 and may have astep ST having a stepped structure. The top sub-electrode 80 may beformed to include a downward protrusion portion PD_D filling theextension region ER of the top storage node electrode hole H2.

Referring to FIG. 23 , the method may include a process of removing aportion of the second preliminary upper supporter pattern 73P to form asecond upper supporter pattern 73 and an opening portion OP. The methodmay include a process of removing the second top mold layer 63 to form acavity CV and etching a portion of the first preliminary upper supporterpattern 71P to form a first upper supporter pattern 71. A process offorming the second upper supporter pattern 73, the opening portion OP,the cavity CV, and the first upper supporter pattern 71 may be the sameas or similar to a process of forming the second lower supporter pattern39, the opening portion OP, the cavity CV, and the first lower supporterpattern 31 described above with reference to FIG. 13 .

Referring to FIG. 24 , the method may include a process of removing thefirst top mold layer 61 to form a cavity CV and removing the upper etchstop layer 50 to form an opening OP between bottom sub-electrodes 40.The first top mold layer 61 and the upper etch stop layer 50 may beremoved by performing a wet etch process having etch selectivity on thelower supporter pattern 30, the upper supporter pattern 70, and thestorage node electrodes 40 and 80. For example, the process of removingthe first top mold layer 61 and the upper etch stop layer 50 may be anLAL lift-off process. At least a portion of the third bottom mold layer25 may be removed together in the process of removing the upper etchstop layer 50. In an embodiment, the process of removing the upper etchstop layer 50 may be a radical dry cleaning process.

As the upper etch stop layer 50 is removed, the top surface of thesecond lower supporter pattern 39, the step ST of the top sub-electrode80, and a portion of the top surface of the bottom sub-electrode 40 maybe exposed. The filler part 50 a of the upper etch stop layer 50 may beremoved, and thus, the opening portion OP of the second lower supporterpattern 39 may be opened again. The side surface of the downwardprotrusion portion PU_D of the top sub-electrode 80, the inclinedsurface SS of the bottom sub-electrode 40, and the top surface of thethird bottom mold layer 25 may be exposed through the opening portionOP. Subsequently, the method may include a process of removing the thirdbottom mold layer 25 and the first bottom mold layer 21 through theopening portion OP.

Referring to FIG. 25 , the method may include a process of forming adielectric layer 90. The dielectric layer 90 may be formed toconformally cover surfaces of the bottom sub-electrode 40, the topsub-electrode 80, the first lower supporter pattern 31, the second lowersupporter pattern 39, the first upper supporter pattern 71, and thesecond upper supporter pattern 73, which are exposed through the openingportion OP and the cavity CV. For example, the dielectric layer 90 mayinclude at least one of metal oxides such as hafnium oxide(Hf_(x)O_(y)), aluminium oxide (Al_(x)O_(y)), titanium oxide(Ti_(x)O_(y)), tantalum oxide (Ta_(x)O_(y)), ruthenium oxide(Ru_(x)O_(y)), lanthanum oxide (La_(x)O_(y)), or zirconium oxide (ZrO₂),a dielectric material having a perovskite structure such as SrTiO₃(STO),(Ba, Sr)TiO₃(BST), BaTiO₃, lead zirconate titanate (PZT), lead lanthanumzirconium titanate (PLZT), silicon oxide, and silicon nitride. Thedielectric layer 90 may be formed by using a process such as a CVDprocess, a PVD process, or an ALD process, where step coverage is good.

Referring again to FIG. 2 , the method may include a process of forminga plate electrode 100, filling the cavity CV and the opening portion OP,on the dielectric layer 90. The plate electrode 100 may include a bottomplate electrode 101 and a top plate electrode 103. The bottom plateelectrode 101 may be formed on the dielectric layer 90. The bottom plateelectrode 101 may conformally cover the dielectric layer 90. Even afterthe bottom plate electrode 101 is formed, a spare space may remain ineach of the cavity CV and the opening portion OP. For example, thebottom plate electrode 101 may include the same material as that of thetop sub-electrode 80 or the bottom sub-electrode 40. The top plateelectrode 103 may cover the bottom plate electrode 101, on the bottomplate electrode 101. The top plate electrode 103 may fill the sparespace of each of the cavity CV and the opening portion OP. For example,the top plate electrode 103 may include SiGe. In an embodiment, theplate electrode 100 may be a single layer. For example, the plateelectrode 100 formed of a single layer may include a refractory metalmaterial such as SiGe, cobalt (Co), titanium (Ti), nickel (Ni), tungsten(W), or a molybdenum (Mo). The plate electrode 100 may include at leastone of metal nitrides such as TiN, TiAlN, and WN.

According to the embodiments, by using an etch stop layer, thesemiconductor device may limit and/or prevent a profile defect fromoccurring in a top storage node electrode. Also, the semiconductordevice may use the etch stop layer in a process of removing a stepheight of a mold layer of a peri region and a cell region, and thus, maylimit and/or prevent the height loss of a storage node electrode,thereby providing a storage node electrode having a high aspect ratio.The semiconductor device may provide the top storage node electrodeincluding a step, and thus, even when misalignment between the topstorage node electrode and a bottom storage node electrode occurs, aprofile defect and a defective connection may not occur, therebyimproving reliability.

While embodiments of inventive concepts have been described withreference to the accompanying drawings, it should be understood by thoseskilled in the art that various modifications may be made withoutdeparting from the scope of inventive concepts and without changingessential features thereof. Therefore, the above-described embodimentsshould be considered in a descriptive sense only and not for purposes oflimitation.

What is claimed is:
 1. A method of manufacturing a semiconductor device,the method comprising: forming a bottom mold structure on a substrate;forming a bottom sub-electrode on the substrate; forming a lowersupporter pattern covering a portion of a side surface of the bottomsub-electrode; forming an etch stop layer covering a top surface of thelower supporter pattern and a top surface of the bottom sub-electrode,the etch stop layer including a filler part extending up to a level thatis lower than a bottom end of the lower supporter pattern; forming apreliminary top mold layer on the etch stop layer; planarizing the etchstop layer and the preliminary top mold layer; forming a top moldstructure on the etch stop layer; forming a top storage node electrodehole passing through the etch stop layer and the top mold structure, thetop storage node electrode hole exposing the top surface of the bottomsub-electrode; forming a top sub-electrode filling the top storage nodeelectrode hole, the top sub-electrode including a step extending in adirection toward an inner portion thereof; and removing the etch stoplayer.
 2. The method of claim 1, wherein a cross-section of the fillerpart has a U-shape or a V-shape.
 3. The method of claim 1, wherein theforming the bottom mold structure includes: forming a first bottom moldlayer and lower supporter layer.
 4. The method of claim 3, wherein theforming the lower supporter pattern includes: forming a preliminarylower supporter pattern by forming a bottom storage node electrode holepenetrating the lower supporter layer; and forming a preliminary lowersupporter pattern including an overhang by forming a lower capping layercovering the preliminary lower supporter pattern.
 5. The method of claim4, wherein the forming the bottom sub-electrode includes: forming anelectrode material layer filling the bottom storage node electrode hole.6. The method of claim 5, wherein the forming the lower supporterpattern includes: forming an opening by removing a portion of thepreliminary lower supporter pattern including the overhang, and forminga cavity by removing the first bottom mold layer.
 7. The method of claim6, wherein the forming the etch stop layer includes: forming a secondbottom mold layer filling the cavity and the opening; re-opening theopening by partially removing the second bottom mold layer; and formingthe etch stop layer in the opening.
 8. The method of claim 7, whereinthe re-opening the opening includes: forming an inclined surface on theupper portion of the bottom sub-electrode by partially etching thebottom sub-electrode.
 9. The method of claim 8, wherein the topsub-electrode further includes: a downward protrusion portion in contactwith the inclined surface.
 10. The method of claim 8, wherein the etchstop layer covers the inclined surface.
 11. The method of claim 1, theforming the top storage node electrode hole further includes: etchingthe top mold structure to form a stepped portion, and the steppedportion is offset with respect to an inner wall of the top storage nodeelectrode hole.
 12. The method of claim 1, the method further includes:forming an upper supporter pattern covering a portion of a side surfaceof the top sub-electrode.
 13. The method of claim 12, the forming theupper supporter pattern includes: forming a preliminary upper supporterpattern by forming the top storage node electrode hole; forming apreliminary upper supporter pattern including an overhang by forming anupper capping layer covering the preliminary upper supporter pattern;and removing a portion of the preliminary upper supporter patternincluding the overhang.
 14. The method of claim 13, the removing theetch stop layer includes: forming a cavity by removing a portion of thetop mold structure through an opening of the upper supporter pattern,and exposing the etch stop layer.
 15. A method of manufacturing asemiconductor device, the method comprising: forming a bottom moldstructure on a substrate; forming a bottom storage node electrode holepenetrating the bottom mold structure and forming a preliminary lowersupporter pattern; forming a bottom sub-electrode in the bottom storagenode electrode hole; forming a lower supporter pattern having an openingby partially removing the preliminary lower supporter pattern; forming abottom mold layer filling the opening; re-opening the opening bypartially removing the bottom mold layer; forming an etch stop layerincluding a filler part partially filling the opening; forming a topmold structure on the etch stop layer; forming a top storage nodeelectrode hole through the etch stop layer and the top mold structure toexpose a top surface of the bottom sub-electrode; forming a topsub-electrode filling the top storage node electrode hole; and removingthe etch stop layer; wherein the top sub-electrode including a stepextending in a direction toward an inner portion thereof, and whereinthe filler part has a U-shape or V-shape in cross section.
 16. Themethod of claim 15, wherein the preliminary lower supporter patternincludes an overhang.
 17. The method of claim 15, the method furtherincludes: before forming the lower supporter pattern, planarizing a topsurface of the preliminary lower supporter pattern and a top surface ofthe bottom sub-electrode.
 18. The method of claim 15, the method furtherincludes: forming a preliminary top mold layer completely filling theopening on the etch stop layer before forming the top mold structure;and exposing a top surface of the etch stop layer by partially removingthe preliminary top mold layer through a planarization process.
 19. Themethod of claim 15, the removing the etch stop layer includes: formingan upper supporter pattern including an opening; and exposing the etchstop layer by removing a portion of the top mold structure through theopening.
 20. A method of manufacturing a semiconductor device, themethod comprising: forming a preliminary lower supporter pattern on asubstrate; forming a bottom sub-electrode on the substrate; forming alower supporter pattern including an opening by partially etching thepreliminary lower supporter pattern; forming an etch stop layer coveringa top surface of the bottom sub-electrode and a top surface of the lowersupporter pattern and filling a portion of the opening; forming apreliminary top mold layer filling the opening; forming a top moldstructure on the etch stop layer and the preliminary top mold layer;forming a top sub-electrode penetrating the top mold structure; andremoving the etch stop layer; forming a dielectric layer covering thelower supporter pattern, the bottom sub-electrode, and the topsub-electrode; and forming a plate electrode in contact with thedielectric layer; wherein the etch stop layer has a U-shape or V-shapein cross section.